Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-1-
CATALYST SYSTEM AND ITS USE IN OLEFIN POLYMERIZATION
FIELD OF THE INVENTION
[001] The present invention relates generally to the field of bulky ligand
metallocene
catalysts and their use for olefins) polymerization. In particular, the
invention is directed
to a catalyst system with enhanced activity, which includes a bulky ligand
metallocene
catalyst compound and a method for preparing such a system. More specifically,
the
present invention is directed to a catalyst system comprising a bulky ligand
metallocene
catalyst compound, an activator compound, a Group 13 element containing first
modifier,
and a cycloalkadiene second modifier, to a method of preparing such a catalyst
system, and
for its use in the polymerization of olefin(s).
BACKGROUND OF THE INVENTION
[002] Numerous catalysts and catalyst systems have been developed that provide
polyolefins with certain advantageous properties. One class of these catalysts
are now
commonly referred to as metallocenes. Metallocenes are broadly defined as
organometallic
coordination complexes containing one or more moieties in association with a
metal atom
from Groups 3 to 17 or the Lanthanide series of the Periodic Table of
Elements. These
catalysts are highly useful in the preparation of polyolefms, allowing one to
closely tailor
the final properties of a polymer.
?0 [003] Although metallocene catalysts are used extensively to obtain
polyolefms with
molecular weight, polydispersity, melt index, and other properties well suited
for a desired
application, the use of these catalysts is expensive. It is therefore an
object of this invention
to increase the activity of metallocene catalyst systems and thereby reduce
the cost
associated with utilizing such a system.
?5 [004] Organoborate and boron compounds are known as activators for olefin
polymerization systems. The use of these compounds as activators, instead of
alumoxane
compounds, to form active olefin polymerization catalysts is documented in the
literature.
Marks (Marks et al. 1991) reported such a transformation for olefin
polymerization using
Group 4 metallocene catalysts containing alkyl leaving groups activated with
30 tris(pentafluorophenyl)borane. Similarly, Chien et al. (1991) activated a
dimethyl
zirconium catalyst with tetra(pentafluorophenyl)borate. However, when Chien
used
methylalumoxane (MAO) as well as the borate for the activation of the dimethyl
zirconium
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
catalyst for the polymerization of propylene, only a small amount of polymer
was
produced.
[005] U.S. Patent No. 5,747,406 discloses an increased catalytic activity when
using
indene or other cycloalkadienes with a half sandwich transition metal catalyst
and MAO as
the activating activator. This catalyst composition demonstrates enhanced
activity in the
polymerization of olefins. For the polymerization of ethylenell-hexene using
indenyl
zirconium tris(diethyl-carbamate), modified MAO and indene, the addition of
indene
increased the activity of the system 3.5 times.
[006] In spite of the advances in the prior art, there exists a need to
provide for a highly
l0 active metallocene catalyst systems, for a method for its preparation and
use in the
polymerization of olefin(s).
SUMMARY OF THE INVENTION
[007] The present invention provides a catalyst system and a method for
preparing a
catalyst system which includes a bulky ligand metallocene catalyst compound,
an activator
L 5 compound, a Group 13 element containing first modifier, and a
cycloalkadiene second
modifier. The first and second modifiers, when utilized together, act to
enhance the activity
of the catalyst system. The present invention also provides a process for
polymerizing
olefins) utilizing the catalyst systems described herein.
DETAILED DESCRIPTION OF THE INVENTION
?0 [008] The present invention provides a metallocene catalyst system having
enhanced
activity, a method for preparing this catalyst system and a method for
polymerizing
olefins) utilizing same. More specifically, the present invention provides for
a catalyst
system which includes a bully ligand metallocene catalyst compound, preferably
a half
sandwich bulky ligand metallocene catalyst compound, an activator compound, a
Group 13
?5 element containing first modifier, and a cycloalkyldiene second modifier.
Bulky Li~and Metallocene Compounds
[009] The catalyst system of the invention includes a bulky lig'and
metallocene catalyst.
Bulky ligand metallocene compounds generally include both half and full
sandwich
compounds having one or more bully ligands bonded to at least one metal atom.
Typical
SO bulky ligand metallocene compounds are generally described as containing
one or more
bulky ligand(s) and one or more leaving groups) bonded to at least one metal
atom. The
bulky ligand metallocene compounds preferred include one unsubstituted or
substituted,
cyclopentadienyl ligand or cyclopentadienyl-type ligand. These types of bullcy
ligand
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-3-
metallocene compounds are also referred to as half sandwich compounds or mono-
cyclopentadienyl compounds (mono-Cps), and the terms are used interchangeably
herein.
[010] The unsubstituted or substituted, cyclopentadienyl ligand or
cyclopentadienyl-type
bully ligand, is generally represented by one or more open, acyclic, or fused
ring or ring
system typically composed of atoms selected from Groups 13 to 16 atoms of the
Periodic
Table of Elements. Preferably the atoms are selected from the group consisting
of carbon,
nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum
or a
combination thereof. The unsubstituted or substituted, cyclopentadienyl
ligands or
cyclopentadienyl-type ligands include heteroatom substituted and/or heteroatom
containing
(0 cyclopentadienyl-type ligands.
[011] Non-limiting examples of these bulky ligands include cyclopentadienyl
ligands,
cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands,
fluorenyl ligands,
octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,
cyclopentacyclododecene ligands,
azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands,
phosphinimine (WO
99/40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands,
borabenzene ligands and
the like, including hydrogenated versions thereof, for example
tetrahydroindenyl ligands.
[012] Bulky ligands which comprise one or more heteroatoms include those
ligands
containing nitrogen, silicon, boron, germanium, sulfur and phosphorous, in
combination
with carbon atoms to form an open, acyclic, or preferably a fused, ring or
ring system, such
?0 as, for example, a hetero-cyclopentadienyl ancillary ligand. Other bulky
ligands include
but are not limited to bulky amides, phosphides, alkoxides, aryloxides,
imides, carbolides,
borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
[013] The cyclopentadienyl ligand or cyclopentadienyl-type bulky ligand may be
unsubstituted or substituted with a combination of substituent groups R. Non-
limiting
?5 examples of substituent groups R include one or more from the group
selected from
hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl
radicals, cycloalkyl
radicals or aryl radicals, acyl radicals, amyl radicals, alkoxy radicals,
aryloxy radicals,
alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals,
aryloxycarbonyl radicals,
carbomoyl radicals, alkyl- or diall~yl- carbamoyl radicals, acyloxy radicals,
acylamino
30 radicals, aroylamino radicals, straight, branched or cyclic, alkylene
radicals, or combination
thereof. In a preferred embodiment, substituent groups R have up to 50 non-
hydrogen
atoms, preferably from 1 to 30 carbon, that can also be substituted with
halogens or
heteroatoms or the like. Non-limiting examples of alkyl substituents R include
methyl,
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-4-
ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl
groups and the
like, including all their isomers, for example tertiary butyl, isopropyl, and
the like. Other
hydrocarbyl radicals include fluoromethyl, fluroethyl, difluroethyl,
iodopropyl,
bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals
including
trimethylsilyl, trimethylgermyl, methyldiethylsilyl aald the like; and
halocarbyl-substituted
organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-
bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and
disubstitiuted
boron radicals including dimethylboron for example; and disubstituted
pnictogen radicals
including dimethylamine, dimethylphosphine, diphenylamine,
methylphenylphosphine,
LO chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy,
methylsulfide and
ethylsulfide. Non-hydrogen substituents R include the atoms carbon, silicon,
boron,
aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like,
including
olefins such as but not limited to olefinically unsaturated substituents
including vinyl-
terminated ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the
like. Also, at
least two R groups, preferably two adjacent R groups, are joined to form a
ring structure
having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous,
silicon,
germanium, aluminum, boron or a combination thereof. Also, a substituent group
R group
such as 1-butanyl may form a carbon sigma bond to the metal M.
[014] The metal atom is preferably selected from Groups 3 through 15 and the
lanthanide
?0 or actinide series of the Periodic Table of Elements. Preferably the metal
is a transition
metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, even more
preferably
the transition metal is from Group 4 and most preferably titanium, zirconium
or hafilium.
[015] In one embodiment,. the half sandwich or mono-Cp bulky ligand catalyst
compounds utilized in the catalyst system of the invention is represented by
Formula I as
?5 set forth below:
LMX"
Formula I
wherein:
30 [016] M is a metal atom from Groups 3 to 15 or the Lanthanide series of the
Periodic Table of Elements, preferably Groups 4, 5 and 6, even more preferably
Group 4 and most preferably Ti, Zr or Hf;
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-5-
[017] L is a substituted or unsubstituted, ~-bonded bully ligand coordinated
to M,
preferably a substituted or unsubstituted cyclopentadienyl or cyclopentadienyl-
type
ligand;
[018] each X is independently hydrogen, an aryl, allcyl, alkenyl, alkylaryl,
or
arylalkyl radical having 1 to 20 carbon atoms, a hydrocarboxy radical having 1
to 20
carbon atoms, a halide, a nitrogen containing radical having 1 to 20 carbon
atoms;
and wherein
[019] the value of n depends upon the valence state of M and is preferably 2,
3 or 4.
[020] In another embodiment, the half sandwich or mono-Cp bulky ligand
catalyst
compounds utilized in the catalyst system of the invention is represented by
Formula II or
Formula III as set forth below:
L
~A >n
Q~U/Q
Y
Z
Formula II
wherein:
[021] M is a metal atom from Groups 3 to 15 or the Lanthanide series of the
Periodic Table of Elements, preferably Groups 4, 5 and 6, even more preferably
Group 4 and most preferably Ti, Zr or Hf;
[022] L is a substituted or unsubstituted, ~-bonded bulky ligand coordinated
to M,
preferably a substituted or unsubstituted cyclopentadienyl or cyclopentadienyl-
type
ligand;
[023] Q can be the same or different and is independently selected from the
group
consisting of -O-, -NR-, -CR2_ and -S-;
~5 [024] Y is either C or S;
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-6-
[025] Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SiR3, -
PR2~ -H, and substituted or unsubstituted aryl group with the proviso that
when Q is -
NR- then Z is selected from the group consisting of -OR, -NR2, -SR, -SiR3, -
PR2
and -H;
[026] n is 1 or 2;
[027] A is a univalent anionic group when n is 2 or A is a divalent anionic
group
when n is 1; when n is 2, A can be the group formed by QQYZ depicted in
formula I
above;
and
[028] As used above, each R can be the same or different and is independently
a
group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus where
one or
more R groups may be attached to the L substituent, preferably R is a
hydrocarbon
group containing from 1 to 20 carbon atoms, most preferably an alkyl,
cycloalkyl or
an aryl group; and
L
-A~n
.Y
Z m
Formula III
~0
wherein:
[029] M is a metal atom from Groups 3 to 15 or the Lanthanide series of the
Periodic Table of Elements, preferably Groups 4, 5 and 6, even more preferably
Group 4 and most preferably Ti, Zr or Hf;
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
[030] L is a substituted or unsubstituted, ~-bonded bulky ligand coordinated
to M,
preferably a substituted or unsubstituted cyclopentadienyl or cyclopentadienyl-
type
ligand;
[031] Q can be the same or different and is independently selected from the
group
consisting of -O-, -NR-, -CR2_ and -S-
[032] Y is either C or S;
[033] Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SiR3, -
PR2~ -H, and substituted or unsubstituted aryl group with the proviso that
when Q is -
NR- then Z is selected from the group consisting of -OR, -NR2, -SR, -SiR3, -
PRA
and -H;
[034] n is 1 or 2;
[035] A is a univalent anionic group when n is 2 or A is a divalent anionic
group
when n is 1; when n is 2, A can be the group formed by QQYZ depicted in
formula II
above;
[036] R can be the same or different and is independently a group containing
carbon, silicon, nitrogen, oxygen, and/or phosphorus where one or more R
groups
may be attached to the L substituent, preferably R is a hydrocarbon group
containing
from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl or an aryl
group;
[037] T is a bridging group selected from the group consisting of an alkylene
or
arylene group containing from 1 to 10 carbon atoms optionally substituted with
carbon or heteroatoms, germanium silicone and alkyl phosphine; and
[038] m is 1 to 7, preferably 2 to 6, most preferably 2 or 3.
[039] In Formula II and III above, the substituent formed by Q, Q, Y and Z is
preferably a
unicharged polydentate ligand exerting electronic effects due to its high
polarizibility,
similar to the cyclopentadienyl group (L) described above. In preferred
embodiments of this
invention, the disubstituted carbamates, shown in Formula IV,
sNl
s
~O
/N~
Formula IV
and the carboxylates, shown in Formula V,
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
_g_
oMv
0
%O
/C~
Formula V
are employed.
[040] Illustartive examples of these mono-Cp bulky ligand metallocene catalyst
compounds are which may be utilized in the catalyst system of the invention
include:
indenyl zirconium tris(pivalate), indenyl zirconium tris(p-toluate), indenyl
zirconium
tris(benzoate), (1-methylindenyl) zirconium tris(pivalate), (2-meth-ylindenyl)
zirconium
tris(diethylcarbamate), (methylcyclopentadienyl) zirconium tris(pivalate),
(cyclopentadienyl)
zirconium tris(pivalate), (pentamethylcyclopentadienyl) zirconium
tris(benzoate), n-
butylcyclopentadienylzirconium trispivalate, (n-butylcyclopenta-
dienyl)tris(benzoate),
(tetrahydroindenyl)zirconium tris(pivalate), (tetrahydroindenyl)zirconium
tris(benzoate),
(tetrahydroindenyl)zirconium tt-is(pentenate), (1,3-
dimethylcyclopentadienyl)zirconium
tris(pivalate), (1,3-methylethylcyclopentadienyl)zirconium tris(pivalate),
tetramethylcyclopentadienyl)zirconium tris(pivalate), (pentamethyl-
cyclopentadienyl)zirconium tris(pivalate),
(cyclopentylcyclopentadienyl)zirconium
tris(benzoate), (benzylcyclopentadienyl)zirconium tris(benzoate), (n-
butylcyclopentadienyl)-
hafnium tris(pivalate), (n-butylcyclopentadienyl)titanimn tris(pivalate).
pentamethyl-
cyclopentadienyltitanium isopropoxide, pentamethylcyclopentadienyltribenzyl
titanium,
dimethylsilyltetramethylcyclopentadienyl-tert-butylamido titaniwn dichloride,
pentamethyl-
cyclopentadienyl titanium trimethyl, dimethylsilyltetramethylcyclopentadienyl-
tert-
butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl-
dodecylamido
hafnium dihydride and dimethylsilyltetramethylcyclopentadienyl-dodecylamido
hafnium
dimethyl. Particularly preferred mono-Cp compounds utilized are 1,3-
dimethylcyclopentadienylzirconium trispivalate and indenylzirconium
trispivalate.
[041] The above mono-Cp bulky ligand metallocene catalyst compounds may be
made
using any conventional process as is well known. W one method of manufacturing
this
catalyst, a source of cyclopentadienyl-type ligand is reacted with a metal
compound of the
formula M(CR2)4 or M(NR2)4 in which M and R are defined above. The resulting
product is
then dissolved in an inert solvent, such as toluene, and the heterocummulene
such as COZ,
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-9-
is contacted with the dissolved product to insert into one or more M-CR2 or M-
NRZ bonds
to form, in this instance, a carboxylate or a carbamate. In another method of
manufacturing
this catalyst is described in WO 00/10709, published January 13, 2000, and
incorporated
herein by reference.
Activator Compounds
[042] The above described polymerization catalyst compounds are typically
activated in
various ways to yield compounds having a vacant coordination site that will
coordinate,
insert, and polymerize olefin(s). The catalyst system of the invention may
include a single
activator compound or a combination of activator compounds. For the purposes
of this
0 patent specification and appended claims, the term "activator" is defined to
be any
compound or component or method which can convert a neutral bulky ligand
metallocene
catalyst compound to a catalytically active bulky ligand metallocene catalyst
cation.
[043] In one embodiment, the catalyst system of the invention includes an
alumoxane as
an activator. Alumoxane activators are generally oligomeric compounds
containing -Al(R)-
5 O- subunits, where R is an alkyl group. Examples of alumoxanes include
methylalumoxane
(MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
Alumoxanes may be produced by the hydrolysis of the respective
trialkylaluminum
compound. MMAO may be produced by the hydrolysis of trimethylaluminum and a
higher trialkylaluminum such as triisobutylaluminum and are generally more
soluble in
:0 aliphatic solvents and more stable during storage. There are a variety of
methods for
preparing alumoxane and modified alumoxanes, non-limiting examples of which
are
described in U.S. Patent No. 4,665,208, 4,952,540, 5,041,584, 5,091,352,
5,206,199,
5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,
5,248,801,
5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253,
5,731,451,
:5 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European
publications EP-
A-0 561 476, EP-Bl-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT
publication WO 94/10180, all of which are herein fully incorporated by
reference.
[044] In another embodiment the catalyst system of the invention includes
modified
methyl alumoxane in heptane (MMA03A) commercially available from Akzo
Chemicals,
.0 Inc., Holland, under the trade name Modified Methylalumoxane type 3A.
[045] In another embodiment, organoaluminum compounds are utilized as
activators.
Non limiting examples of suitable organoaluminum activator compounds include
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-10-
trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,
tri-n-
octylaluminum and the like.
[046] In another embodiment, other suitable activators which may be utilized
are
disclosed in WO 98/09996, incorporated herein by reference, which describes
activating
bulky ligand metallocene-type catalyst compounds with perchlorates, periodates
and iodates
including their hydrates. WO 98/30602 and WO 98/30603, incorporated by
reference,
describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate)~4THF as an
activator for a
bulky ligand metallocene catalyst compound.
[047] In another embodiments, the catalyst system of the invention may include
activators
such as those disclosed in WO 99/18135, which describes the use of organo-
boron-
aluminum acitivators, EP-B1-0 781 299 which describes using a silylium salt in
combination with a non-coordinating compatible anion, both incorporated herein
by
reference. Additional methods of activation such as using radiation (see EP-Bl-
0 615 981
herein incorporated by reference), electro-chemical oxidation, and the like
are also
contemplated as activating methods for the purposes of rendering the neutral
bulky ligand
metallocene catalyst compound or precursor to a bulky ligand metallocene
ration capable of
polymerizing olefins. Other activators or methods for activating a bulky
ligand
metallocene-type catalyst compound are described in for example, U.S. Patent
Nos.
5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99142467
(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)
benzimidazolide), which
are herein incorporated by reference. Still other activators include those
described in PCT
publication WO 98/07515 such as tris (2, 2', 2"- nonafluorobiphenyl)
fluoroaluminate, also
incorporated herein by reference. Combinations of activators are also
contemplated by the
invention, please see for example, EP-Bl 0 573 120, PCT publications WO
94/07928 and
WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410 all of which are
fully
incorporated herein by reference.
Modifiers for the Catalyst System
[048] The catalyst system of the present invention also includes a Group 13
element
containng f rst modif er and a cycloalkadienyl second modifier which, when
utilized
together, act to enhance the activity of the catalyst system.
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-11-
Group 13 Element Containing First Modifier
[049] In one embodiment, the first modifier is utilized in the catalyst system
of the present
invention includes a cation and an anion component, and is represented by
Formula VI
below:
(L'-H)a+ (Aa-)
Formula VI
[050] wherein L' is an neutral Lewis base;
[051] H is hydrogen;
[052] (L'-H)+ is a Bronsted acid
[053] Ad- is a non-coordinating anion having the charge d-
[054] d is an integer from 1 to 3.
[055] The cation component, (L-H)a+ may include Bronsted acids such as protons
or
protonated Lewis bases or reducible Lewis acids capable of protonating ox
abstracting a
moiety, such as an akyl or aryl, from the bullcy ligand metallocene catalyst
compound,
resulting in a cationic transition metal species.
[056] W one embodiment the cation component (L-H)d+ includes amrnoniums,
oxoniums,
phosphoniums, silyliums and mixtures thereof, preferably ammoniums of
methylamine,
aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
trimethylamine,
triethylamine, N,N- dimethylaniline, methyldiphenylamine, pyridine, p-bromo
N,N-
dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from
triethylphosphine,
triphenylphosplune, and diphenylphosphine, oxomiuns from ethers such as
dimethyl ether
diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such
as diethyl
thioethers and tetrahydrothiophene and mixtures thereof. In a preferred
embodiment, the
cation component (L-H)a+ of the first modifier is dimethylanaline.
[057] In another embodiment cation component (L-H)d+ may also be an
abstracting moiety
such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures,
preferably
carboniums and ferroceniums. In a preferred embodiment, the cation component
(L-H)d+ of
the first modifier is triphenyl carbonium.
[058] In another embodiment, the anion component Aa- of the first modifier
includes those
anions having the formula [Mk+Qn]a- wherein k is an integer from 1 to 3; n is
an integer
from 2 to 6; n - k = d; M is an element selected from Group 13 of the Periodic
Table of the
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-12-
Elements and Q is independently a hydride, bridged or unbridged diallcylamido,
halide,
alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,
substituted
halocarbyl, and halosubstituted-hydrocarbyl radicals, with Q having up to 20
carbon atoms
with the proviso that in not more than 1 occurrence is Q a halide. In a
preferred
embodiment, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon
atoms, more
preferably each Q is a fluorinated aryl group, arid most preferably each Q is
a pentafluoryl
~.yl group.
[059] In another embodiment, the anion component Ad- of the first modifier may
also
include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is
fully
incorporated herein by reference.
[060] In another embodiment the first modifier is a tri-substituted boron,
tellurium,
aluminum, gallium, or indium compound or mixtures thereof. The three
substituent groups
are each independently selected from alkyls, alkenyls, halogen, substituted
alkyls, aryls
arylhalides, alkoxy and halides. Preferably, the three groups are
independently selected
from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls,
and alkenyl
compounds aald mixtures thereof, preferred are alkenyl groups having 1 to 20
carbon
atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20
carbon
atoms and aryl groups having 3 to 20 carbon atoms (including substituted
aryls). In another
embodiment, the three groups are alkyls having 1 to 4 carbon groups, phenyl,
napthyl or
mixtures thereof. In another embodiment each of the three substituent groups
is a
fluorinated hydrocarbyl group having,l to 20 carbon atoms, preferably a
fluorinated aryl
group, and more preferably a pentafluoryl aryl group. In another embodiment
the first
modifier is trisperfluorophenyl boron or trisperfluoronapthyl boron.
[061] In another embodiment the first modifier or activity promoter is an
organometallic
compound such as the Group 13 organometallic compounds ofU.S. Pat. Nos.
5,198,401,
5,278,119, 5,407,884, 5,599,761 5,153,157, 5,241,025, and WO-A-93/14132, WO-A-
94/07927, and WO-A-95/07941, all documents are incorporated herein by
reference.
[062] In. another embodiment, the first modifier is selected from
tris(pentafluorophenyl)-
borane (BF-15), dimethylanilinium tetra(pentafluorophenyl)borate (BF-20),
dimethylanilinium tetra(pentafluorophenyl)aluminate, dimethylanilinium
tetrafluoroaluminate, tri(n-butyl)ammonium) tetra(pentafluorophenyl)borate,
tri(n-
butyl)ammonium) tetra(pentafluorophenyl)aluminate, tri(n-butyl)ammonium)
tetrafluoroaluminate, the sodium, potassium, lithium, tropyliun and the
triphenylcarbenium
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-13-
salts of these compounds, or from combinations thereof. In preferred
embodiment, the first
modifier is N,N-dimethylanilinium tetra(perfluorophenyl)borate or
triphenylcarbenium
tetra(perfluorophenyl)borate.
Cycloalkadienyl Second Modifier
[063] The use of a second modifier in combination with first modifiers in the
catalyst
system of the invention significantly enhances the catalyst system's activity.
[064] In one embodiment, the second modifier or activity promotor utilized in
the catalyst
system a cycloalkadiene compound. A cycloall~adiene is an organocyclic
compound having
two or more conjugated double bonds, examples of which include cyclic
hydrocarbon
compounds having 2 to 4 conjugated double bonds and 4 to 24, preferably 4 to
12, carbons
atoms. The cycloalkadiene may optionally be substituted with a group such as
alkyl or aryl
of 1 to 12 carbon atoms.
[065] Examples of activity enhancing cycloalkadienes include unsubstituted and
substituted cyclopentadienes, indenes, fluorenes, and fulvenes, such as
cyclopentadiene,
methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene,
hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-
dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-
tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-
indene, 4,7-
dimethylindene, 4,5,6,7-tetrahydroindene, fluorene, methylfluorene,
cycloheptatriene,
methylcycloheptatriene, cyclooctatraene, methylcyclooctatraene, fulvene and
dimethyl-
fulvene. These compounds may be bonded through an alkylene group of 2-8,
preferably 2-
3, carbon atoms, such as for example bis-indenylethane, bis(4,5,6,7-tetrahydro-
1-
indenyl)ethane, 1,3-propanedinyl-bis(4,5,6,7-tetrahydro)indene, propylene-
bis(1-indene),
isopropyl(1-indenyl) cyclopentadiene, diphenylmethylene(9-fluorenyl),
cyclopentadiene
and isopropylcyclopentadienyl-1-fluorene. Preferred cycloalkydienes are the
1,3-type
dimes such cyclopentadiene and indene.
[066] In the catalyst system of this invention, the addition of the first and
second
modifiers, described above, have been found to have a synergistic effect on
the catalytic
activity of a bulky ligand metallocene mono-Cp/MAO catalyst component. When
the first
modifier, for example BF-20, is used alone, no enhancement of the
polymerization activity
occurs, and when the second modifier, for example indene, is used alone as a
modifier the
enhancement is not as significant as when both are utilized together. It is
therefore axi
aspect of the present invention that the activity of the catalyst system for
the polymerization
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-14-
of olefins is enhanced relative to the activity of the same catalyst system
without the
addition of the Group 13 element containing and the cycloalkadiene modifiers.
In one
embodiment of the invention, the activity of the catalyst system is increased
at least 200%,
more preferably at least 400%, more preferably 600%, more preferably at least
700%, more
preferably at least 800%, more preferably at least 900%, or more preferably at
least 1000%
relative to the activity of the same catalyst system to which no modifier has
been added.
[067] In one embodiment, each of the modifiers are added in an amount
necessary to
effect an increase in the catalyst systems activity. In another embodiment,
the molar ratio
of the Group 13 element containing first modifier to the metal contained in
the bulky ligand
metallocene catalyst compound is about 0.01 to 100, preferably about 0.01 to
10, more
preferably 0.05 to 5 and even more preferably 0.1 to 2Ø In another
embodiment, the molar
ratio of the cycloalkadiene secondlmodifier to the metal contained in the
bulky ligand
metallocene catalyst compound is about 0.01 to 100, preferably about 0.01 to
10, more
preferably about 0.05 to 5, and even more preferably 0.1 to 2Ø
Polymerization Process
[068] The catalyst system of the invention described above is suitable for use
in any
polymerization process over a wide range of temperatures and pressures. The
temperatures
may be in the range of from -60 °C to about 280°C, preferably
from 50°C to about 200°C,
and the pressures employed may be in the range from 1 atmosphere to about 500
~0 atmospheres or higher.
[069] Polymerization processes include solution, gas phase, slurry phase and a
high
pressure process or a combination thereof. Particularly preferred is a gas
phase or slurry
phase polymerization of one or more olefins at least one of which is ethylene
or propylene.
[070] In one embodiment, the process of this invention is directed toward a
solution, high
~5 pressure, slurry or gas phase polymerization process of one or more olefin
monomers
having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more
preferably 2
to 8 carbon atoms. Polyolefms that can be produced using these catalyst
systemss include,
but are not limited to, homopolymers, copolymers and terpolymers of ethylene
and higher
alpha-olefins containing 3 to about 12 carbon atoms, such as propylene, 1-
butene, 1-
30 pentene, lrhexene, 4-methyl-1-pentene, and 1-octene, with densities ranging
from about
0.86 to about 0.97; polypropylene; ethylene/propylene rubbers (EPR's);
ethylene/propylene/diene terpolymers (EPDM's); and the like.
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-15-
[071] Other monomers useful in the process of the invention include
ethylenically
unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or
nonconjugated
dimes, polyenes, vinyl monomers and cyclic olefins. Non-limiting monomers
useful in the
invention may include norbornene, norbornadiene, isobutylene, isoprene,
vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene
norbornene,
dicyclopentadiene and cyclopentene.
[072] In the most preferred embodiment of the process of the invention, a
copolymer of
ethylene is produced, where with ethylene, a comonomer having at least one
alpha-olefin
having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and
most
preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process.
[073] Typically in a gas phase polymerization process a continuous cycle is
employed
wherein one part of the cycle of a reactor system, a cycling gas stream,
otherwise known as
a recycle stream or fluidizing medium, is heated in the reactor by the heat of
polymerization. This heat is removed from the recycle composition in another
part of the
cycle by a cooling system external to the reactor. Generally, in a gas
fluidized bed process
for producing polymers, a gaseous stream containing one or more monomers is
continuously cycled through a fluidized bed in the presence of a catalyst
under reactive
conditions. The gaseous stream is withdrawn from the fluidized bed and
recycled back into
the reactor. Simultaneously, polymer product is withdrawn from the reactor and
fresh
monomer is added to replace the polymerized monomer. (See for example U.S.
Patent Nos.
4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,
5,453,471,
5,462,999, 5,616,661 and 5,668,228, all of which are fully incorporated herein
by
reference.)
[074] The reactor pressure in a gas phase process may vary from about 60 psig
(690 kPa)
to about 500 psig (3448 kPa), preferably in the range of from about 200 psig
(1379 kPa) to
about 400 psig (2759 kPa), more preferably in the range of from about 250 psig
(1724 kPa)
to about 350 psig (2414 lcPa).
[075] The reactor temperature in a gas phase process may vary from about
30°C to about
120°C, preferably from about 60°C to about 115°C, more
preferably in the range of from
about 70°C to 110°C, and most preferably in the range of from
about 70°C to about 95°C.
[076] Other gas phase processes contemplated by the process of the invention
include
series or multistage polymerization processes. Also gas phase processes
contemplated by
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-16-
the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818
and
5,677,375, and European publications EP-A- 0 794 200 EP-B1-0 649 992, EP-A- 0
802 202
and EP-B- 634 421 all of which are herein fully incorporated by reference.
[077] In a preferred embodiment, the reactor utilized in the present invention
is capable
and the process of the invention is producing greater than 500 lbs of polymer
per hour (227
Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably
greater than
1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540
Kg/hr), even
more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more
preferably greater than
35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000
lbs/hr (22,700
Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to
greater than
100,000 lbs/hr (45,500 Kg/hr).
(078] A slurry polymerization process generally uses pressures in the range of
from about
1 to about 50 atmospheres and even greater and temperatures in the range of
0°C to about
120°C. W a slurry polymerization, a suspension of solid, particulate
polymer is formed in a
liquid polymerization diluent medium to which ethylene and comonomers and
often
hydrogen along with catalyst are added. The suspension including diluent is
intermittently
or continuously removed from the reactor where the volatile components are
separated from
the polymer and recycled, optionally after a distillation, to the reactor. The
liquid diluent
employed in the polymerization medium is typically an alkane having from 3 to
7 carbon
ZO atoms, preferably a branched alkane. The medium employed should be liquid
under the
conditions of polymerization and relatively inert. When a propane medium is
used the
process must be operated above the reaction diluent critical temperature and
pressure.
Preferably, a hexane or an isobutane medium is employed.
[079] A preferred polymerization technique of the invention is referred to as
a particle
ZS form polymerization, or a slurry process where the temperature is kept
below the
temperature at which the polymer goes into solution. Such technique is well
known in the
art, and described in for instance U.S. Patent No. 3,248,179 which is fully
incorporated
herein by reference. Other slurry processes include those employing a loop
reactor and
those utilizing a plurality of stirred reactors in series, parallel, or
combinations thereof.
30 Non-limiting examples of slurry processes include continuous loop or
stirred tank
processes. Also, other examples of slurry processes are described in U.S.
Patent No.
4,613,484, which is herein fully incorporated by reference.
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-17-
[080] In an embodiment the reactor used in the slurry process of the invention
is capable
of and the process of the invention is producing greater than 2000 lbs of
polymer per hour
(907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most
preferably
greater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry
reactor used in
the process of the invention is producing greater than 15,000 lbs of polymer
per hour (6804
Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000
lbs/hr
(45,500 Kg/hr).
[081] Examples of solution processes are described in U.S. Patent Nos.
4,271,060,
5,001,205, 5,236,998 and 5,589,555, which are fully incorporated herein by
reference
[082] A preferred process of the invention is where the process, preferably a
slurry or gas
phase process is operated in the presence of a bulky ligand metallocene
catalyst system of
the invention and in the absence of or essentially free of any scavengers,
such as .
triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-
hexylaluminum and
diethyl aluminum chloride, dibutyl zinc and the like. This preferred process
is described in
PCT publication WO 96/08520 and U.S. Patent No. 5,712,352 and 5,763,543, which
are
herein fully incorporated by reference.
Polymer Products
[083] The polymers produced by the process of the invention can be used in a
wide
variety of products and end-use applications. The polymers produced by the
process of the
invention include linear low density polyethylene, elastomers, plastomers,
high density
polyethylenes, low density polyethylenes, polypropylene and polypropylene or
polyethylene copolymers.
[084] The polymers of the invention may be blended and/or coextruded with any
other
polymer. Non-limiting examples of other polymers include linear low density
polyethylenes produced via conventional Ziegler-Natta and/or bulky ligand
metallocene
catalysis, elastomers, plastomers, high pressure low density polyethylene,
high density
polyethylenes, polypropylenes and the like.
[085] The preferred polymers of this invention contain at least SO%
polyethylene.
Comonomers such as 1-butene, 1-pentane, 1-hexane, benzylcyclobutante and
styrene axe
preferred. The preferred polymer product will have a density of from 0.85 to
0.96 g/cc,
more preferably from about 0.88 to 0.96 g/cc and most preferably from about
0.90 to 0.96
g/cc.
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-18-
[086] Polymers produced by the process of the invention and blends thereof are
useful in
such forming operations as film, sheet, and fiber extrusion and co-extrusion
as well as blow
molding, injection molding and rotary molding. Films include blown or cast
films formed
by coextrusion or by lamination useful as shrink film, cling film, stretch
film, sealing films,
oriented films, snack packaging, heavy duty bags, grocery sacks, baked and
frozen food
packaging, medical packaging, industrial liners, membranes, etc. in food-
contact and non-
food contact applications. Fibers include melt spinning, solution spiraling
and melt blown
fiber operations for use in woven or non-woven form to make filters, diaper
fabrics,
medical garments, geotextiles, etc. Extruded articles include medical tubing,
wire and cable
coatings, geomembranes, and pond liners. Molded articles include single and
mufti-layered
constructions in the form of bottles, tanks, large hollow articles, rigid food
containers and
toys, etc.
Examples
[087] In order to provide a better understanding of the present invention
including
representative advantages thereof, the following examples are offered.
[088] The Activity values, shown in Table 1, are normalized values based upon
grams of
polymer produced per mmol of transition metal in the catalyst per hour per 100
psi (689
KPa) of ethylene polymerization pressure.
[089] 1H NMR spectra were measured by a Bruker AMX 300
[090] Polydispersity Index (PDI) is equivalent to Molecular Weight
Distribution
(Mw/Mn, where Mw is weight average molecular weight and Mn is number average
molecular weight), as determined by gel permeation chromatography.
[091] Methylalumoxane (MAO) was used in toluene (30 wt%). (BF-20) is
dimethylanilinium tetra(pentafluorophenyl)borate (BF-20). Catalyst Component A
isl,3
dimethylcyclopentadienylzirconium trispivalate and Catalyst Component B is
indenyl
zirconium trispivalate.
Example 1 Synthesis of (1,3-Dimethylcyclopentadienyl)zirconium trispivalate
(Catalyst Component A)
[092] To a solution of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride
(1.390 g,
3.99 mmol) axed pivalic acid (1.520 g, 14.9 mmol) in toluene at 25°C.
was added neat
triethylamine (1.815 g, 18.10 mmol) with stirring. A white precipitate formed
immediately
which was removed by filtration. The compound was isolated as a pale-yellow
powder in
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-19-
88% yield and exhibited purity above 99% based on NMR results. 1H NMR (toluene-
d8):
X5.84 (m, 2H), 5.53 (m, 1H), 2.18 (s, 6H), 1.13 (s, 27H).
Example 2 Preparation of Indenylzirconium Trisnivalate (Catalyst
Component B)
[093] The compound (h~d)Zr(NEta)3 (37 mg, 0.088 mmole) was dissolved in 1.0 mL
of
benzene-d6. A solution of pivalic acid (27 mg, 0.26 xnmole) in 1.0 mL benzene-
d6 was
added with stirring. ~H NMR exhibited resonances assigned to NEt2 H and
(Ind)Zr(02
CCMe3)3. 1H NMR (C6 D6) d 7.41 (AA'BB', indenyl, 2H), 6.95 (AA'BB', indenyl,
2H), 6.74
(t, J=3.3 Hz, 2-indenyl, 1H), 6.39 (d, J=3.3 Hz, 1-indenyl, 2H), 1.10 (s, CH3,
27H).
Example 3 Polymerization Process
[094] Utilizing the catalyst compounds prepared in Examples 1 and 2,
polyethylene was
produced in a slurry phase reactor.
[095] For each of Component A and B prepared in Examples 1 and 2, a solution
in
toluene (0.0036M) was prepared. An aliquot (O.Sml) of this solution was added
to a 6
ounce (177m1) bottle containing an aliquot (0.2m1) of MAO in toluene (3.15M).
An aliquot
(0.6m1) of indene in toluene (0.0030M) then an aliquot (1.0 ml) of BF-20 in
toluene
(0.0018M) was added to the mixing bottle. Anhydrous conditions were
maintained. The
polymerization time for all the Examples 1 and 2 was 30 minutes. Table 1 below
shows the
catalyst composition makeup for Examples 1 and 2.
[096] The slurry reactor was a 1.65 liter, stainless steel autoclave equipped
with a
mechanical agitator. The reactor was first dried by heating at 96°C
under a stream of dry
nitrogen for 40 minutes. After cooling the reactor to 50°C, 1000 ml of
hexane was added
and the reactor components were stirred under a gentle flow of nitrogen.
Rexene-1 (20m1)~
was added to the reactor as well as an aliquot of triisobutylaluminum in
hexane (0.5 ml,
0.86M) to act as a scavenger. The temperature of the reactor was gradually
raised to 70°C
and the reactor was pressured to 150psi (1034K.Fa) with ethylene. The pre-
mixed catalyst
solution prepared above was then inj ected into the reactor to start the
polymerization.
Heating was continued until a polymerization temperature of 85°C was
attained. Unless
otherwise noted, polymerization was continued for 30 minutes, during which
time ethylene
was continually added to the reactor to maintain a constant pressure. At the
end of 30
minutes, the reactor was vented and opened.
CA 02428855 2003-05-08
WO 02/40555 PCT/USO1/42459
-20-
Comparative Examine 4 - Comuarative Runs Cl-C6
[097] hl Comparative Runs C1 to C6, polyethylene was produced under conditions
similar
to those of Examples 1 and 2 with the exception that the mixture of indene and
BF-20 was
not used. The polymerization time for each run in Example 4 was 30 minutes.
[098] The catalyst system activity, the molecular weights (Mw and Mn), the
molecular
weight distributions (Mw/Mn, also known as PDT of various polyethylene made in
from
the catalyst compounds prepared in the Examples shown in Table 1. As shown in
Table 1,
the catalyst systems of the invention comprising the Group 13 element
containing first
modifier and the cycloalkadiene second modifier possessed significantly higher
activity.
TABLE 1
Example CatalystIndene/ZrBF-20/Zr~1(MAO)/ZrActivityMw Mn PDI
or molar molar molar
run ratio ratio ratio
C1 A - - 420 15058 427424123358 3.5
C2 A - 1.0 420 14431 395835142874 2.8
C3 A 1.0 - 420 66525 364033122111 3
1 A 1.0 1.0 420 20029622239154609 4.1
C4 B - - 420 12549 29079290980 3.2
CS B - 1.0 420 14379 295051102456 2.9
C6 B 1.0 - 420 28078 412101166874 2.5
2 B 1.0 1.0 420 99921 20715158686 3.5
